Low foaming washing and cleansing agents



United States Patent M US. Cl. 252170 10 Claims ABSTRACT OF THEDISCLOSURE This invention relates to low foaming washing and cleansingcompositions comprising a content of:

(A) polymers of (3-hydroxymethyl-3-ethyl)-oxacyclobutane containingp'olyoxyalkylene radicals selected from the group consisting of (1)compounds of the formula wherein x is an integer of from 5 to 12, m isan integer of from 2 to 16, n is an integer of from 1 to 8 and the ratioof m to n is between about 1.5 to 1 and 10 to 1; and

(B) surface-active polyoxyalkylene polymers containing oxyalkylene unitsselected from the group consisting of oxyethylene units and oxypropyleneunits, said polymers containing from 2 to 90 oxypropylene units, theamount of oxypropylene units in said polymer being more than 50 molpercent of the total number of said oxyalkylene units.

CLAIM OF PRIORITY Priority based on the corresponding German patentapplication H 58,255, filed Jan. 15, 1966, is hereby claimed under theprovisions of 35 U.S.C. 119.

THE PRIOR ART In an increasing measure, mechanical washing methods arebeing employed to wash china, glass, porcelain, ceramic, metal andsynthetic articles. Detergents containing specific surface-activecompounds are generally utilized. These detergents should be lowfoaming, so that they do not affect the function of the washingapparatus. A foam formation of too large a volume, caused and increasedby the vigorous motion of the bath in the machine, leads to considerabletrouble, a the foam mass decreases the mechanical effect of the liquidsprayed onto the articles tobe cleaned and furthermore may cause thebath in the machine to run over.

Recently, developments in washing apparatus have been directed towardfurther increasing the intensity of the liquor motion as well as thewater volume cycled per minute, and in this way to further improve themechanical cleansing effect. As a result of such developments, it wasfound that conventional washing agents, such as alkylene oxide adducts,were no longer satisfactory under these turbulent washing conditions.Instead, due to volu- 3,499,841 Patented Mar. 10, 1970 minous foamformation, the conventional washing agents gave rise to thedisadvantages mentioned previously.

It is an object of this invention to provide novel compositions ofwashing and cleansing agents having either low foaming properties or nofoaming properties at all, which compositions are particularly suitedfor the me chanical washing of china.

Another object of the invention is to obtain low foaming washing andcleansing compositions comprising a content of:

(A) Polymers of (3-hydroxymethy1-3-ethy1)-oxacyclobutane containingpolyoxyalkylene radicals selected from the group consisting of (1)compounds of the formula wherein at is an integer of from 5 to 12, m: isan integer of from 2 to 16, n is an integer of from 1 to 8 and the ratioof m to n is between about 1.5 to 1 and 10 to 1; and

(B) Surface-active polyoxyalkylene polymers containing oxyalkylene unitsselected from the group consisting of oxyethylene units and oxypropyleneunits, said polymers containing from 2 to oxypropylene units, the amountof oxypropylene 'units in said polymer being more than 50 mol percent ofthe total number of said oxyalkylene units.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

DESCRIPTION OF INVENTION These objects have been attained by employing acombination of non-ionic agents comprising a content of:

(A) Polymers of (3-hydroxymethyl-3-ethyl)-oxacyclobutane containingpolyoxyalkylene radicals of the general formula wherein x represents anynumber from 5' to 12, m represents any number from 2 to 16, n representsany number from 1 to 8, and the ratio of m to n is between about 1.5 to1 and 10to 1; and

(B) Surface-active compounds with a content of oxypropylene radicals orpolyoxypropylene radicals containing 2 to 90 oxypropylene units, andpreferably with a further content of oxyethylene radicals orpolyoxyethylene radicals, the amount of oxypropylene units in the totalnumber of the oxyalkylene units being more than 50 mol percent.

These combinations of non-ionic agents possess a remarkable cleansing,degreasing and draining effectiveness and due to their low formingproperties, they are particularly suitable for mechanical washing andcleaning methods.

The preparation of compound A of the new non-ionic compositions isstarted by polymerization of (3-hydroxymethyl-3-ethyl)-oxacylclobutane.These compounds are obtained from the monomeric oxacyclobutanederivative by polymerization in the presence of acid catalysts,according to the method described in the published German patentapplication (Auslegeschrift) No. 1,023,227. The average number ofmonomer units in the polymer is between and 12, preferably between 7 and10.

The further reaction to obtain polymers containing the respectivepolyoxyalkylene radicals is effect d in a generally known manner byaddition of ethylene oxide or of propylene oxide and ethylene oxide, inthe presence of alkaline catalysts such as sodium hydroxide, sodiummethylate and the like, preferably under pressure. Based on the monomerunit, about 2 to 16, preferably 4 to mols of ethylene oxide, possiblyafter the preliminary addition of 1 to 8, preferably 3 to 5 mols ofpropylene oxide, are added. In the polyoxyalkylenated polymer, the molarratio of propylene oxide to ethylene oxide amounts preferably to about0.3 to 0.7 oxypropylene units to 1 oxyethylene unit.

Examples for compounds of component A are: the adduct of 4, 6 or 8 molsof ethylene oxide, based on the monomer unit, to apoly-(3-hydroxymethyl-3-ethyl)-oxacyclobutane having a polymerizationdegree of 7 to 10; as well as the addition products of 3 mols ofpropylene oxide and 10 mols of ethylene oxide, or 4 mols of propyleneoxide and 8 mols of ethylene oxide, or 6 mols of propylene oxide andmols of ethylene oxide, based on the monomer unit, to apoly-(3-hydroxymethyl-3-ethyl)-oxacyclobutane having a polymerizationdegree of 7 to 10.

The A components are readily water soluble, possess tensidecharacteristics, and tend in themselves to give a more voluminous foamformation. The turbidity points are preferably above 35 C.

As compounds of component B are primarily propylene oxide polymers asobtained by polymerization of propylene oxide or by addition ofpropylene oxide to compunds containing at least two reactive hydrogenatoms, in particular low molecular weight aliphatic or aromaticcompounds with from 2 to 6 carbon atoms containing hydroxyl or aminogroups. The reaction is effected in known manner in the presence ofalkaline catalysts, preferably under pressure. These known propyleneoxide polymers have a total molecular weight of 1000 to 5000, preferably1700 to 4100. Preferably, up to mol percent of ethylene oxide, based onthe total amount of alkylene oxides, may be added to these propyleneoxide polymers.

Examples of propylene oxide polymers of the known kind are: the adductof 4.5 mols of ethylene oxide to a polypropylene glycol with a molecularweight of 1740; the adduct of 7 or 16 mols of ethylene oxide to apolypropylene glycol with a molecular weight of 2750; the adduct of 8.5mols of ethylene oxide to a polypropylene glycol consisting of 56oxypropylene radicals; the adduct of mols of propylene oxide toglycerin; and the adduct of 48 mols of propylene oxide and 7 mols ofethylene oxide to ethylene diamine.

Another method for the preparation of suitable compounds of component Bconsists in the addition of 1 to mols of propylene oxide to highmolecular weight aliphatic or aliphatic-aromatic compounds with 8 to 22carbon atoms containing hydroxyl or amino groups, preferably afterpreliminary addition of as much as 20 mols of ethylene oxide. In thelatter case, the portion of the propylene oxide to the total amount ofthe alkylene oxide is more than 50 mol percent, preferably 55 to 80 molpercent. The aliphatic compounds possess higher molecular weightradicals with 8 to 22, and preferably 10 to 20 carbon atoms and arepreferably of the formula wherein R represents a radical having from 8to 36 carbon atoms selected from the group consisting of alkyl, alkenyl,alkadienyl and hydroxy-alkenyl, H represents a replaceable hydrogen andY represents a bridging link selected from the group consisting of NH,O, S, -CONH,

4 -SO NH, and CO-O. The aliphatic-aromatic compounds possess highermolecular weight radicals with 12 to 22, and preferably 14 to 18 carbonatoms and are preferably of the formula wherein Y and H have theabove-assigned values and R' represents a radical having 12 to 22 carbonatoms selected from the group consisting of alkylphenyl, alkylnaphthyl,alkoxyphenyl and alkylcyclohexyl. The hydrocarbon radicals R and R maycontain conventional substitutents such as hydroxyl groups, halideatoms, or alkyl side chains.

As starting compounds for the preparation of the above, the followingmay be utilized: higher molecular weight aliphatic alcohols, carboxylicacids, mercaptans, amines, carboxylic acid amides or alkanolamides,sulfonic acid amides and the like, as well as alkylphenols.

Examples of these compounds are: the adduct of 7 mols of ethylene oxideand 10 mols of propylene oxide or of 9 mols of ethylene oxide and 16mols of propylene oxide to a fatty alcohol admixture of the chainlengths C -C the adduct of 4 mols of ethylene oxide and 12 mols ofpropylene oxide to oleyl alcohol; the adduct of 7 mols of ethylene oxideand 10 mols of propylene oxide to nonylphenol; and the adduct of 10 molsof ethylene oxide and 20 mols of propylene oxide to nonylphenol.

Finally, the B component can be prepared by addition to 1 to 6 mols ofethylene oxide and 2 to 20 mols of propylene oxide to polymers of(3-hydroxymethyl-3-ethyl)-oxacyclobutane, as they were also used asstarting materials for the preparation of the A components. Theindicated molar amounts are based on the monomer unit of the polymer.The amount of the propylene oxide in the total amount of the alkyleneoxides has to be more than 50 mol percent, preferably 55 to mol percent.

Examples for compounds of the indicated type are: the adducts of 3 molsof ethylene oxide and 6 mols of propylene oxide, or of 3 mols ofethylene oxide and 10 mols of propylene oxide, or of 4 mols of ethyleneoxide and 5 mols of propylene oxide, or of 4 mols of ethylene oxide and10 mols of propylene oxide, based on the monomer unit, to apoly-(3-hydroxymethyl-3-ethyl)-oxacyclobutane having a polymerizationdegree of 7 to 10.

The portions of the individual components in the washing and cleansingcompositions of the invention are, in general, 70 to 98% by weight ofthe A components, and 2 to 30% by weight of the B components. In thepractice, particularly mixtures of to by weight of the A components andof 5 to 15% by weight of the B components have proved useful. Theamounts used of these mixtures in the cleansing bath are within theconcentration range of about 0.05 to 0.5 g./l., preferably 0.1 to 0.4g./l. based on the total amount of the components A and B.

The composition of the mixtures can be varied within the amount ratioindicated without losing the specific advantage of low foamingproperties. Since the component A, which is inclined to a voluminousfoam formation, is responsible for the cleaning and wetting effect, aswell as for the draining and the clear-drying appearance of the washedchina, it has to be recognized as a special advantage that the foam canalready be reduced to a sufficient degree with the addition of verysmall amounts of the B components of the mixture.

Concentrated liquid products, such as those preferably used fordishwashers equipped with automatic metering devices, may be prepared bydissolving the mixtures of the invention in water, if so desired underconcomitant usage of organic water-miscible solvents or by dissolvingthe mixtures in organic solvents. These concentrates contain about 20 to85% of the mixture of A and B components. By varying the constituents,these liquid concentrates may be standardized in such a manner that theypossess good temperature stability and that they are not inclined toprecipitate or separate into layers. In corresponding manner, thedehydration temperature of the mixtures of the invention in aqueoussolution can be varied and adjusted to the respective requirements, forexample, for the rinsing temperature utilized. The utmost low foamingstate of the mixtures of the invention is generally attained only whenthe dehydration temperature of the mixtures is below the rinsingtemperature, preferably below 40 C.

The following specific embodiments of the invention are illustrativethereof. It is obvious, however, that other expedients may be employedand these specific embodiments are not to be deemed limitative in anymanner.

EXAMPLES The foam behavior of various non-ionic tensides and mixtures ofwashing agents was examined for purpose of comparison in a special foamexamination apparatus The test results, given in the following table,show the extraordinarily favorable foam behavior of the mixtures of theinvention.

The foam apparatus used was constructed in similar manner as a moderndishwasher operating according to the spray system. By means of arotating pump about 170 liters of water per minute were rotated andsprayed into the metering chamber by means of a rotating spray armequipped with nozzles. Foam heights from to 280 mm. may be measured inreproducible manner, whereas larger foam volumes cannot be measuredaccurately and, therefore, they are indicated in the table as 280. Thebath temperature during the tests was 50 C.; the hardness of the waterused was 16 dH and the duration of the foam test lasted five minutes.The reading of the foam heights was conducted immediately after theapparatus became idle and 30 seconds thereafter. This foam apparatus isdescribed in Fette, Seifen, Anstrichmittel, 66 (1964), 529 (Fats, Soaps,Paints).

The letters A and B indicate the components corresponding to thedescriptive text.

TAB LE Foam height in mm. 30 sec.

end of run Foam height in min. at the end of run Ex. No.

1a..-. (A) Polymer tenside having a polymerization degree of 7 to 10,adducted with 4 mols of ethylene oxide. 1b...- (A) Polymer tensidehaving a polymerization degree of 7 to 10, adduioited with 4 mols ofethylene ox e. (B) Fatty alcohol 012-014 adducted with 9 mols ofethylene oxide and 11 mols of propylene oxide.

Cone, g./l.

Composition of Mixture 2a (A) Polymer tenside having a po- 0.12lymerization degree of 7 to 10, adducted with 6 mols of ethylene oxide.

2b.... (A) Polymer tenside having a polymerization degree of 7 to 10,adducted with 6 mols of ethylene ox e. (B) Adduct of 6 mols of ethyleneoxide to a polypropylene glycol of a molecular weight of 2,250. 2a.....(A) Polymer tenside having a polymerization degree of 7 to 10, adductedwith 6 mols of ethylene oxide.

(B) Nonylphenol adducted with 9 mols of ethylene oxide and 10 mols ofpropylene oxide.

Foam Foam height height nmm. in mm. 30sec. at the after Ex. Cone end ofend of No. Composition of Mixture g./l. run run 2f (A) Polymer tensidehaving a po- 0.12

lymerization degree of 7 to 10, adducted with 6 mols of ethylene ox1de.(B) Polymer tenside having a po- 0.008 20 0 lymerization degree of 7 to10, adducted with 4 mols of ethylene oxide and 5 mols of propyleneoxide.

3-- (A) Polymer tenside having a po- 0.12

lymerization degree of 7 to 10, adducted with 4 mols of propylene oxideand 8 mols of ethylene oxide. (B) Fatty alcohol 012-014 adducted 0.00820 0 with 9 mols of ethylene oxide and 11 mols of propylene oxide.

Example 4 A concentrated liquid rinsing agent suitable for commercialdishwashers was prepared having the following composition PercentPolymer tenside having a polymerization degree of 7 to 10, adducted with6 mols of ethylene oxide 75 Fatty alcohol C -C adducted with 9 mols ofethylene oxide and 11 mols of propylene oxide 5 Ethanol 20 The productdeveloped practically no foam at all at application temperatures between50" C. and C.

After a complete alkaline cleansing of the china in the main wash cycle,the water for the second rinsing was supplemented with concentrations of0.2 to 0.3 g./l. of the above composition. Spotless dishes with a clearluster were thus obtained.

Example 5 A very low foaming washing agent for household dishwashers wasprepared having the following composition:

Percent Polymer tenside having a degree of polymerization of 7 to 10,adducted with 6 mols of ethylene oxide 53 Adduct of 4.5 mols of ethyleneoxide to a polypropyleneglycol having a molecular weight of 1750 l3Ethanol 17 Water 17 At an application concentration of 0:2 to 0.4 g./l.,a satisfactory clear-dry effect is obtained on the Washed articlesutilizing the above composition.

The preceding specific embodiments are illustrative of the invention. Itis obvious, however, that other expedients known to those skilled in theart may be employed without departing from the spirit of the invention.

We claim:

1. Low foaming Washing and cleansing compositions consisting essentiallyof a content of:

(A) from 70% to 98% by weight of a polymer of (3hydroxymethyl-3-ethyi)-oxacycl.obutane containing polyoxyalkyleneradicals selected from the group consisting of (1) compounds of theformula and (2) compounds of the formula [-CHpO-CHz-O-hCH20(CsHe0)n(C2H40)mH wherein x is an integer of from 5 to 12, m is aninteger of from 2 to 16, n is an integer of from 1 7 to 8 and the ratioof m to n is between about 1.5 to 1 and to 1; and

(B) from 2% to 30% by weight of surfaceactive polyoxyalkylene polymerscontaining oxyalkylene units selected from the group consisting ofoxyethylene units and oxypropylene units, said polymers containing from2 to 90 oxypropylene units, the amount of oxypropylene units in saidpolymer being more than 50 mol percent of the total number of saidoxyalkylene units.

2. The low foaming washing and cleansing compositions of claim 1 whereinsaid component A is present in an amount of from 85% to 95% by weightand said component B is present in an amount of from 5% to by weight.

3. The low foaming washing and cleansing compositions of claim 1 whereinsaid component B is a polyoxyalkylene polymer selected from the groupconsisting of polyoxypropylene glycols having a molecular weight of from1000 to 5000 and polyoxypropylene glycols having a molecular weight offrom 1000 to 5000 adducted with up to 30%, based on the total amount ofoxyalkylene units, of ethylene oxide.

4. The low foaming washing and cleansing compositions of claim 3 whereinsaid molecular weight of said polyoxypropylene glycol is from 1700 to4100.

5. The low foaming washing and cleansing composition of claim 1 whereinsaid component B is a high molecular lipophilic radical having from 8 tocarbon atoms and a replaceable hydrogen atom selected from the groupconsisting of compounds of the formula wherein R represents a memberselected from the group consisting of alkyl, alkenyl, alkadienyl andhydroxyalkenyl, R represents a member selected from the group consistingof alkylphenyl, alkylnaphthyl, alkoxyphenyl and alkylcyclohexyl, Yrepresents a bridging link selected from the group consisting of NH, O,S, CONH, -SO NH and COO--, and H represents a replaceable hydrogen atom,adducted with 50 mol percent to 100 mol percent of oxyproplyene unitsand the remainder of oxyethylene units.

6. The compositions of claim 5 wherein said high molecular weightlipophilic radicals having replaceable hydrogen atoms are aliphatic andcontain from 10 to 20 carbon atoms.

7. The compositions of claim 5 wherein said high molecular weightlipophilic radicals having replaceable hydrogen atoms arealiphatic-aromatic and contain from 14 to 18 carbon atoms.

8. The low foaming washing and cleansing composi tions of claim 1wherein said component B is an alkylene oxide adduct of a polymer of(3-hydroxymethyl-3-ethyl)- oxacyclobutane having a polymerization degreeof from 5 to 12, said polymer adducted with from 1 to 6 mols of ethyleneoxide and from 2 to 20 mols of propylene oxides, based on the monomerunits, from to 80 mol percent of the alkylene oxide units in the adductbeing propylene oxide units.

9. Liquid low foaming composition consisting essentially of from 20% toby weight of the low foaming washing and cleaning compositions of claim1 in solution in a solvent media selected from the group consisting ofwater, water-miscible lower alcohols and mixtures thereof.

10. The method of rinsing of solid articles which comprises rinsing saidsolid articles with water containing from 0.05 to 0.5 gram per liter ofthe low foaming, washing and cleansing composition of claim 1.

References Cited UNITED STATES PATENTS 2,677,700 5/1954 Jackson et a1.252-89 2,828,345 3/1958 Spriggs 252-89 2,886,600 5/1959 Horsley et al.260-615 2,944,982 7/1960 De Groote et al. 260615 2,948,757 8/1960 Pruittet al. 260615 3,031,510 4/1962 Crecelias 35289 LEON D. ROSDOL, PrimaryExaminer W. SCHULZ, Assistant Examiner US. Cl. X.R.

